Allyl carbonate and substituted allyl carbonate esters of 1,4-dialkylol cyclohexane, and polymers thereof

ABSTRACT

Disubstituted cyclohexane compositions designated as either bis(2-alkylallylcarbonyldioxy) 1,4-dialkylene cyclohexane or bis(2-arylallylcarbonyldioxy) 1,4-dialkylene cyclohexane represented by the formula:   WHEREIN R1 is a lower alkyl and R2 is hydrogen or an alkyl, aryl, aralkyl or alkaryl hydrocarbon radical, are useful in the production of polymers and copolymers. Compositions containing these polymers and copolymers when combined with the proper filler have outstanding stain resistance as well as excellent impact resistance and other strength properties when compared with prior art compositions recognized as outstanding for use in dinnerware.

United States Patent Berry et al.

[54] ALLYL CARBONATEAND SUBSTITUTEDALLYL CARBONATE ESTERS OF1,4-DIALKYLOL CYCLOHEXANE, AND POLYMERS THEREOF [72] Inventors: David A.Berry, Columbus; Gilbert M.

Gynn, Hilliard, both of Ohio [73] Assignee: Dart Industries Inc., LosAngeles, Calif.

22 Filed: July 22, I969 [21] Appl. No.: 843,83]

Chemical Abstracts 64, 17,7 l 7 c (1966) [451 July 25, 1972 PrimaryExaminer- Lewis Gotts Assistant Examiner-Diana G. Rivers AnorneyFred S.Valles and Richard A. Dannells. Jr.

[57] ABSTRACT Disubstituted cyclohexane compositions designated aseither bis(2-alkylallylcarbonyldi0xy) 1,4-dialkylene cyclohexane orbis(Z-arylallylcarbonyldioxy) l,4-dialkylene cyclohexane represented bythe formula:

wherein R is a lower alkyl and R is hydrogen or an alkyl, aryl, aralkylor alkaryl hydrocarbon radical, are useful in the production of polymersand copolymers. Compositions containing these polymers and copolymerswhen combined with the proper filler have outstanding stain resistanceas well as excellent impact resistance and other strength propertieswhen compared with prior art compositions recognized as outstanding foruse in dinnerware.

2 Claims, No Drawings ALLYL CARBONATE AND SUBSTITUTED ALLYL CARBONATEESTERS OF 1,4-DIALKYLOL CYCLOI'IEXANE, AND POLYMERS THEREOF BACKGROUNDOF THE INVENTION l. Field of the Invention This invention is directed toa novel class of monomers and polymers and to a method for theirpreparation. More particu- I O larly, the invention relates todisubstituted cyclohexane monomers and polymers thereof.

The polymers and copolymers derived from the monomeric compositions ofthis invention when reinforced with certain types of fibrous materialssuch as cellulose, glass and polyester fibers, have been found to beideal for use in dinnerware, i.e., flatware including cups, saucers,plates and the like, and in laminated table, bar and counter tops.

2. Description of the Prior Art Melamine-formaldehyde resins which haveDescription widespread use in molded articles, such as dinnerware, haveas their major disadvantage that of being susceptible to various kindsof stains from coffee, tea, fruit and vegetable juices of all types,soft drinks and the like. It would be desirable, if new compositionswere available that have the same impact resistance and other strengthproperties as the conventional melamine-type resinS, but are more stainresistant.

SUMMARY OF THE INVENTION Polymers derived from the disubstitutedcyclohexane monomers of this invention when filled with certain fibrousmaterials and converted to molded articles have high impact resistanceand hardness and have greatly improved stain resistance when compared tothe prior art compositions.

An object of the present invention is to provide monomers and polymersthereof for use in molding compounds and the like. Another object ofthis invention is to provide a process for producing monomericintermediates for producing thermosetting resins useful in dinnerwareand laminated table tops.

The present invention provides a disubstituted cyclohexane compositionrepresented by the formula:

wherein R, is a lower alkyl and R, is hydrogen or alkyl, aryl, aralkylor alkaryl hydrocarbon radical.

The monomeric compositions of this invention are prepared by reacting la 1,4-dialkanol cyclohexane having the formula:

IIMOH wherein R, is a lower alkyl having one to five carbon atoms;

and (2) ally] haloformate or a substituted allyl haloformate having theformula:

wherein R, is H or an alkyl, aryl, aralkyl or alkaryl hydrocarbonradical and X is chloro, bromo or iodo. The reaction is carried out inthe presence of an acid acceptor at a temperature in the range of about5 to about 25 C and a pressure of atmospheric up to psig for a period ofone-half hour to several hours. A suitable acid acceptor is pyridine,although other organic bases can be used such as collidine and dimethylaniline as well as quaternary bases, e.g., trimethyl phenyl ammoniumhydroxide and inorganic bases, e.g., sodium hydroxide.

The reaction is illustrated by the following equation:

lIhOII As indicated by the above equation, the reactants are generallymixed in the stoichiometrical proportion of 2 moles of the substitutedallyl haloformate to 1 mole of the dialkanol cyclohexane. However, thereaction can be suitably carried out using 2 to 5 moles of thehaloformate to 1 mole of the dialkanol cyclohexane.

PREFERRED EMBODIMENTS OF THIS INVENTION In the preferred monomericcomposition of this invention, R, is a C, alkyl and R is H resulting ina structure designated as bis(allylcarbonyldioxy) 1,4-dimethylenecyclohexane:

Other compositions contemplated by this invention and illustrated byspecific examples include the following compositions: bis(2-octylallylcarbonyldioxy) l,4-dimethylene cyclohexane:

bis( 2-phenylallylcarbonyldioxy) l ,4-dimethylene cyclohexane:

O ?Hz0-O-C Hg-C (CnH5)=C Hz Homopolymers and copolymers derived from thedisubstituted cyclohexane monomeric compositions are also provided inaccordance with this invention. The disubstituted cyclohexane monomersof this invention polymerize in the presence of a free-radical initiatorto form a cross-linked, thermosetting resin.

The disubstituted cyclohexane monomers of this invention areprepolymerized in the presence of a suitable solvent such as dioxanewith a suitable initiator, i.e., a peroxide initiator such asdi-tertiary butyl perbenzoate, ditertiary butyl peroxide, di-benzoylperoxide, dilauroyl peroxide, cyclohexanone peroxide, tertiary-butylhydroperoxide, di-acetyl peroxide, dibenzoyl peroxide, cumenehydroperoxide, dicumyl peroxide and the like, at a temperature of about25 to 160 C. for a sufficient period of time to polymerize 10 to 50weight percent, preferably 20 to 35 weight percent of the monomer toprepolymer. The resulting prepolymer product solution is then a cooledand precipitated with a non-solvent and the resulting product isseparated from the liquid phase and dried.

A molding composition is then prepared from the prepolymer by intimatelyblending about 25 to 75 weight percent of theprepolymer of thebis(2-alkylallylcarbonyldioxy) 1,4-dialkylene cyclohexane or bis(2-arylallylcarbonyldioxy) l,4-dialkylene cyclohexane and at least 25weight percent of one or more reinforcing fillers. The reinforcingfillers comprise about l() to 40 weight percent of a primary filler andto 40 weight percent of a secondary filler.'The primary filler consistsof alpha cellulose, glass fibers or polyester fibers or mixturesthereof. The secondary filler consists of clay, calcium carbonate,magnesium, or silica powder or mixtures thereof.

A particularly preferred composition of this invention which isespecially suitable for dinnerware applications consist of:

a. at least 35 weight percent of the polymer which consists of at least50 percent of bis(allylcarbonyldioxy) l,4- dimethylene cyclohexane,

b. about to 40 weight percent of alpha cellulose, and

c. about 10 to 40 weight percent of silica powder, wherein the total ofthe (b) and (c) components are equal to at least 40 percent based on theweight of the final composition. This particular composition has beenfound to have a stain resistance of less than 10 expressed as a colorchange in R units on the Gardner Color Difference Meter. A specificexample of these compositions and results therefrom are set forth in theexamples below.

Copolymers derived from the disubstituted cyclohexane monomericcompositions of this invention have also been found to have greatutility in molding compositions and the like. Typical comonomers thatcan be copolymerized by the same method described above, with thedisubstituted cyclohexane monomers of this invention include vinylaromatics, diallyl carbonates, diallyl phthalates, derivatives thereofand the like. Typical vinyl aromatics include styrene,alpha-methylstyrene, vinyltoluene and substituted styrene and mixturesthereof. The copolymeric compositions comprise 50 to 90 percent byweight of bis(2-alkylallylcarbonyldioxy) or The molding compositions areprepared by dissolving the prepolymer of the disubstituted cyclohexaneor the copolymer derived therefrom in a suitable solvent such asacetone. To the resulting solution is added the desired filler, one ormore of the peroxide initiators and a metallic stearate as a processingaid such as zinc, magnesium, calcium and sodium stearate. In addition tothese components,-other components which can be added to incorporatethem into the compositions of this inventiOn include pigments,delustrants, plasticizers, flame retardant materials and other materialsknown in the art to modify the chemical and physical properties of thefinished molding compositions.

The mixture resulting from the combination of the above components isallowed to dry to remove the solvent. The resulting solid compositioncan then be ground or otherwise reduced into discrete particles and soldas a molding compound or molded into the desired articles.

The examples below illustrate the method of preparation of thecompositions of the present invention, their subsequent polymerizationand copolymerization and their blending with fillers to produce moldingcompounds.

EXAMPLE 1 This example illustrates the preparation of thebis(allylcarbonyldioxy) 1,4-dimethylene cyclohexane monomericcomposition in which l44.2 grams (1 mole) of 1,4-dimethylol cyclohexaneand 250 grams (3.16 moles) of pyridine were charged to a vessel equippedwith a stirrer, thermometer and dropping funnel. After thel,4-dimethylol cyclohexane was dissolved in the pyridine and thetemperature of the solution was cooled to 3 C., allyl chloroformate wascontinuously added to the solution by means of the dropping funnel overa period of about 4% hours while the reaction temperature was maintainedat a temperature in the range of 5 to 8 C. with constant agitation. Thereaction was continued for a period of one hour at temperatures in therange of 3 to 5 C. after the addition of a total of 253.1 grams (2.]moles) of allyl chloroformate. The product mixture was then allowed towann up to room temperature, i.e., about 22 C., and 700 ml of distilledwater containing'about 10 grams of NaCl were added to the reactionmixture. The resulting dimethylene cyclohexane product was separated,washed with distilled water and dried over CaCl,. The product waspurified by a vacuum distillation at temperatures ranging from l56 C. atabout 2 mm Hg to 184 C. at 7.8 mm Hg. The product was repurified byredistilling under the same vacuum conditions to form a light yellowliquid which crystallized upon standing at room temperature. Theresulting product was found to have a hydroxyl number of 97 KOH/gm ofproduct.

EXAMPLE 2 The l4-dimethylol cyclohexane and allylchloroforrnate werereacted as described in Example 1 and the resulting reaction product wasfiltered leaving a brownish-orange filtrate.

The filtrate was vacuum distilled to obtain a clear yellow The productmixture was cooled to 020 C. and mixed with methanol at 0-20 C. toprecipitate the dimethylenc cyclohexane prepolymer. The solid prepolymerwas separated from the liquid phase and repeatedly redissolved inacetone to remove all of the solvent. The polymer was then dried, groundinto a pale yellow powder which was further dried in a vacuum oven for 2days.

EXAMPLE 3 This example illustrates the preparation of a filled moldingcomposition containing the prepolymer obtained from Example 2. 48 grams(about 70.8 percent based on the weight of the final composition) of thedimethylene cyclohexane prepolymer of Example 2 were dissolved in 35grams of acetone. The following components were then added to thesolution: 1.44 grams of TiO,. pigment, 0.98 grams of zinc stearate toserve as a processing aid, 1.44 grams of t-butyl perbenzoate and 16grams (about 23.6 percent based on the weight of the final composition)of alpha cellulose flock sold under the trade name Solka Flock SW 40 andblended in an Atlantic Research Twin-Cone Mixer.

The resulting mixture was dried in a warm vacuum chamber for about 16hours to remove the acetone. The dried material was then further blendedin a two-roll rubber mill for a period of about 5 minutes until it waswell mixed. The resulting material was then broken into small pieces andcompression molded at a temperature of about 320 F. and a pressure of4,000 psi. Compression molded samples were prepared by placing theresulting material in molds under the above conditions for periods of 2,4 and 6 minutes, respectively, and found to have average RockwellHardness values on the M" Scale in the range of 84 to 87. In addition,cups were molded from the composition of this example and measured forcoffee stain resistance. The coffee stain-resistance test comprisedplacing samples of the moldings in a bath of cofi'ee containing twoteaspoons/cup of fresh instant coffee at 180 F. for a period of 48hours. The degree of staining was measured by determining the color ofthe samples before and after exposure to the coffee bath with a GardnerColor Difference Meter. The cups from the composition of this Exampleresulted in a final color change of 8.0 expressed in R units whichmeasures whiteness, from the specimens initial color. This color changecan be compared to the color change of about 43 for articles molded fromstandard melamine-formaldehyde resins.

EXAMPLE 4 This example illustrates the preparation of a copolymercontaining 90 weight percent of the disubstituted cyclohexanecomposition and weight percent of diallyl carbonate. Eight grams ofbenzoyl peroxide was dissolved in 200 grams of dioxane to which wasadded 180 grams of the dimethylene cyclohexane monomer of Example 1.Twenty grams of diallyl carbonate monomer were then slowly added to thesolution. The solution was heated from 22 to 75 C. in two hours andmaintained at a temperature in the range of about 75 to 85 C. for aperiod of about 2% hours to copolymerize about 28% by weight of thecomonomers to the copolymer. The product mixture was cooled to 30 C andmixed with methanol at 0 C. to precipitate the copolymer. The solidcopolymer was then separated from the liquid phase and dried.

EXAMPLE 5 This example illustrates the preparation of a moldingcomposition following the same procedure as Example 3 above except thatthe copolymer formed by the procedure of Example 4 was blended into theformulation set forth in Table I below:

Alpha cellulose 1617 (23.6%) Total 145.7

Based on the weight of the final composition The resulting mixture wascompression molded at about 300 F. and 3,200 psi for 2, 4, 6 and 8minutes, respectively, and was found to have average Rockwell Hardnessvalues on the M Scale in the range of about 99 to 102. Compressionmolded samples of compositions of this example at 6 minute mold timeswere immersed in coffee containing 98 grams of fresh instant coffee in7,000 ml of water for a period of 48 hours results indicated a finalcolor change of 4.8 expressed in R, units by the Gardner ColorDifference Meter.

EXAMPLE 6 This example illustrates a molding composition in which thedimethylene cyclohexane prepolymer formed by the procedure of Example 2was blended with a primary and a secondary filler. The same procedurefollowed in Example 3 was followed in this example to produce a moldingcomposition having the formulation set forth in the table below:

COMPONENTS GRAMS Prepolymer 38.0 (45.5%?" Acetone 75.0

TiO, 3.6

Zinc Stearate 0.5

t-butyl perbenzoate 1.0

Silica Flour" 27.0 (32.3%) Alpha cellulose 13.5 (16.17%)"* Total 158.6

*Prepolymer of bis(allylcarbonyldioxy) 1,4-dimethylene cyclohexane byprocedure of Example 2.

Having a 325 mesh screen analysis by U.S. Standard Sieve Analysis. Basedon the weight of the final composition.

Compression molded samples of the compositions of this example at moldtimes of 2, 4 and 6 minutes, respectively, were found to have averageRockwell Hardness values in the range of to 81. Compression moldedsamples at 6 minute mold times were placed in the same coffee bath asindicated in Example 5 and were found to have color difference on the R,Scale of 9.5.

The foregoing examples have shown the unexpected utility of the novelmonomeric compositions of this invention. In particular, they show theunexpected improvement in the stain resistance of the compositions whenincorporated into molding compositions as compared with standardcommercial grades of melamine-formaldehyde resins. In addition, thehardness values for the present compositions are on the same high levelas the melamine-type resins which make them ideally suited fordinnerware applications.

What is claimed is:

1. A disubstituted cyclohexane composition represented by the formula:

wherein R is a lower alkyl and R is hydrogen or an alkyl, aryl, aralkylor alkaryl hydrocarbon radical.

2. The composition of claim 1 wherein R, is a C alkyl and R is hydrogen.

2. The composition of claim 1 wherein R1 is a C1 alkyl and R2 ishydrogen.